Methods for making sulfonated poly(phenylene ether) and articles made therefrom

Patent metadata

Field	Value
Publication number	US-12398238-B2
Application number	US-202017613862-A
Country	US
Kind code	B2
Filing date	May 13, 2020
Priority date	Jun 18, 2019
Publication date	Aug 26, 2025
Grant date	Aug 26, 2025

Abstract

A method for sulfonation of poly(phenylene ether) can comprise: dissolving a poly(phenylene ether) comprising 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl ether units, or a combination thereof in a mixture of 1,2-dichloroethane and a cosolvent to form a solvent mixture in a mixing vessel, wherein the cosolvent comprises at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, or tetramethylene sulfone; combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate; wherein the sulfonated poly(phenylene ether) has a sulfonation level of 20 to 50%.

First claim

What is claimed is:

1. A method for sulfonation of poly(phenylene ether), comprising
dissolving a poly(phenylene ether) comprising 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl ether units, or a combination thereof, in 1,2-dichloroethane and a cosolvent to form a solvent mixture in a mixing vessel, wherein the cosolvent comprises methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, tetramethylene sulfone, or a combination thereof;
combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form sulfonated poly(phenylene ether);
precipitating the sulfonated poly(phenylene ether); and
filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate;
wherein the sulfonated poly(phenylene ether) has a sulfonation level of 20 to 50%.

2. A method for sulfonation of poly(phenylene ether), comprising:
determining the desired sulfonation level;
if the desired sulfonation level is greater than 20% then dissolving a poly(phenylene ether) comprising 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl ether units, or a combination thereof, in 1,2-dichloroethane and a cosolvent to form a solvent mixture in a mixing vessel, wherein the cosolvent comprises methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, tetramethylene sulfone, or a combination thereof;
combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form sulfonated poly(phenylene ether);
precipitating the sulfonated poly(phenylene ether); and
filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate, and
if the desired sulfonation level is less than or equal to 20% then dissolving poly(phenylene ether) in a solvent mixture comprising 1,2-dichloroethane and greater than 1 to 10 wt % of a cosolvent, wherein the weight percentages are based upon 100 wt % of the solvent mixture, to form a solvent mixture in a mixing vessel; then combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate.

3. The method of claim 1 , wherein the cosolvent comprises ethyl acetate, tetramethylene sulfone, or a combination thereof.

4. The method of claim 1 , wherein the cosolvent comprises ethyl acetate.

5. The method of claim 1 , wherein the cosolvent is ethyl acetate.

6. The method of claim 1 , wherein the dissolving is at a temperature of 30° C. to 60° C.

7. The method of claim 1 , wherein the solvent mixture comprised:
1 to 20 wt % of the poly(phenylene ether);
80 to 99 wt % of the 1,2-dichloroethane; and
1 to 10 wt % of the cosolvent;
wherein the weight percentages are based upon 100 wt % of the solvent mixture.

8. The method of claim 1 , wherein the solvent mixture comprised:
1 to 10 wt % of the poly(phenylene ether);
70 to 90 wt % of the 1,2-dichloroethane; and
1 to 10 wt % of the cosolvent;
wherein the weight percentages are based upon 100 wt % of the solvent mixture.

9. The method of claim 1 , further comprising recovering the solvent and the cosolvent.

10. The method of claim 9 , wherein recovering the solvent and the cosolvent comprises decantation of the filtrate, to form an organic stream, and distilling the organic stream.

11. The method of claim 9 , further comprising recycling the solvent and the cosolvent to the mixing vessel.

12. The method of claim 1 , wherein the sulfonation level is 25% to 50% as determined by NMR.

13. The method of claim 1 , wherein the sulfonated poly(phenylene ether) has a uniform sulfonation level of 20 to 50% as determined by NMR.

14. The method of claim 11 ,
wherein greater than 97 wt % of the 1,2-dichloroethane is recycled; and/or
wherein greater than 95 wt % of the cosolvent is recycled.

15. The method of claim 1 , wherein the cosolvent is present from greater than 1 to 10 wt % wherein the weight percentage are based upon 100 wt % of the solvent mixture.

16. The method of claim 1 , wherein the cosolvent is present from greater than 2 to 6 wt % wherein the weight percentage are based upon 100 wt % of the solvent mixture.

17. The method of claim 1 , wherein the solvent mixture comprised:
5 to 10 wt %, of the poly(phenylene ether);
80 to 90 wt % of the 1,2-dichloroethane; and
2 to 6 wt % of the cosolvent;
wherein the weight percentages are based upon 100 wt % of the solvent mixture.

18. A method for sulfonation of poly(phenylene ether), comprising
dissolving a poly(phenylene ether) comprising 2,6 dimethyl 1,4-phenylene ether units, 2,3,6 trimethyl-1,4-phenylene ether units, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl ether units, or a combination thereof, in 1,2-dichloroethane and optionally a cosolvent to form a solvent mixture in a mixing vessel;
combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form sulfonated poly(phenylene ether);
precipitating the sulfonated poly(phenylene ether); and
filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate;
wherein the sulfonated poly(phenylene ether) has a uniform sulfonation level of 20 to 50% as determined by NMR.

19. A method for sulfonation of poly(phenylene ether), comprising:
determining a desired sulfonation level;
if the desired sulfonation level is greater than 20% then dissolving a poly(phenylene ether) comprising 2,6 dimethyl 1,4-phenylene ether units, 2,3,6 trimethyl-1,4-phenylene ether units, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl ether units, or a combination thereof, in 1,2-dichloroethane and optionally a cosolvent to form a solvent mixture in a mixing vessel;
combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form sulfonated poly(phenylene ether);
precipitating the sulfonated poly(phenylene ether); and
filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate, and
if the desired sulfonation level is less than or equal to 20% then dissolving poly(phenylene ether) in 1,2-dichloroethane and optionally a cosolvent to form a solvent mixture in a mixing vessel; then combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate;
wherein the sulfonated poly(phenylene ether) has a uniform sulfonation level as determined by NMR.

Assignees

• Shpp Global Tech Bv

Inventors

• Chowdhury Rajesh
• Tk Senthil

Classifications

• B01D71/5223

  Polyphenylene oxide, phenyl ether polymers or polyphenylethers · CPC title

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• H01M8/1025

  having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters · CPC title

• C08J2371/12

  Polyphenylene oxides · CPC title

• C08J5/2256

  based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation · CPC title